JP3169984B2 - Thermoplastic saturated norbornene-based polymer molded article having cured layer and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a norbornene-based polymer molded article having a cured layer having excellent adhesion strength and high hardness on its surface, and a method for producing the same. The present invention also relates to the molded article having good adhesive strength after a durability test and capable of forming a cured layer with reduced or eliminated residual solvent, and a method for producing the same. The molded article obtained by the production method of the present invention is particularly suitable as an optical material.

[0002]

2. Description of the Related Art Hitherto, polycarbonate (PC) and polymethyl methacrylate (PMMA) have been mainly used as transparent plastic molding materials for optical devices such as optical disk substrates and plastic lenses. However, PC has a large birefringence, and PMMA has a large water absorption and an insufficient heat resistance, which makes it difficult to meet increasingly sophisticated requirements.

Recently, thermoplastic saturated norbornene-based polymers, such as hydrogenated ring-opening polymers of norbornene-based monomers and addition polymers of norbornene-based monomers and ethylene, have attracted attention as optical plastic molding materials for optical disk substrates and the like. (Japanese Patent Laid-Open No. 60-2)
Nos. 6024, 64-24826, 60-16870
8, No. 61-115912, No. 61-120816). The thermoplastic saturated norbornene-based polymer has excellent transparency, small birefringence, and excellent heat resistance and water absorption resistance, and is a very useful material for optical use. further,
The polymer has strength, water resistance, electrical insulation, solvent resistance,
It also has excellent chemical resistance to acids and alkalis, and is useful as an electrical insulating material, as well as a moisture-resistant packaging material for containers and films, in addition to optical applications. However, a molded article made of a thermoplastic saturated norbornene-based polymer usually has a pencil hardness of 1 (JIS K-5400; 1 kg load).
It has a low surface hardness of about 2H even if it is hard.

[0004] In general, a plastic molded product may require a high surface hardness depending on the use. For example, in the case of an optical disk such as a compact disk and a laser disk, if the surface of the optical disk is scratched by contact with a human hand or another substance, an error occurs in which the content of the recorded memory is incorrectly read. Further, in the fields of optical applications and packaging containers, if the surface of the molded article is damaged, the transparency is reduced. For this reason, a hardened layer may be provided on the surface of the plastic molded product to improve the surface hardness. By providing a cured layer on the surface of a transparent plastic molded product, the transparency and aesthetics of the plastic can be maintained for a long period of time, and excellent chemical resistance and stain resistance can be imparted, leading to expansion of the application range of plastics. In addition to replacing glass, it is possible to develop a variety of applications such as automotive parts, electrical and electronic equipment-related parts, building materials, and furniture.

In order to provide a cured layer on a plastic molded product, a method of applying various curing agents has been adopted. General-purpose curing agents include silicone-based curing agents and organic-based curing agents. Silicone-based curing agents are partial hydrolysates of silane compounds and require heat-curing at a relatively high temperature of about 1 hour at 120 ° C. Therefore, plastic substrates are slightly deformed by heat and precision is required. It is not suitable for plastic molded products. The organic curing agent includes a type in which a melamine-based, alkyd-based, urethane-based, and acrylic-based paint is cured by heating, and a type in which a polyfunctional acrylic-based paint is cured by ultraviolet rays. The former is easy to handle, but has the disadvantage of being inferior in hardness and weather resistance. The latter is
It has excellent hardness and productivity, and is hardened by ultraviolet rays, so it hardly affects the plastic substrate. Therefore, the latter ultraviolet curing agent is suitable as a curing agent for a transparent plastic molded article. The ultraviolet curing agent is generally an acrylic photopolymerizable composition containing a polyfunctional acrylic monomer and / or oligomer, a photopolymerization initiator, and other additives, and without a solvent or diluted with a solvent (thinner).

[0006] By the way, even if an attempt is made to provide a cured layer on a thermoplastic saturated norbornene-based polymer molded article, the molded article has poor wettability with a general-purpose curing agent and has insufficient adhesion.
There is a problem that the cured layer after curing is easily peeled off from the molded product. For example, even if a commercially available non-solvent or an ultraviolet curing agent diluted with a solvent is applied to a thermoplastic saturated norbornene-based polymer molded product, the adhesiveness between the cured layer after curing and the molded product is poor, and the molded product is easily peeled off. . this is,
Because the thermoplastic saturated norbornene polymer has poor surface wetting and high chemical resistance, it does not diffuse across the interface between the cured layer and the other layer, causing entanglement of molecules. Because it is difficult.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a thermoplastic saturated norbornene-based polymer molded article having a cured layer having excellent adhesive strength and high hardness, and a method for producing the same. Another object of the present invention is to provide a thermoplastic saturated norbornene-based polymer molded article having good adhesive strength after a durability test, capable of forming a cured layer in which a residual solvent caused by a curing agent is reduced or eliminated, and a method for producing the same. To provide.

The inventors of the present invention have conducted intensive studies to overcome the problems of the prior art, and as a result, after performing a plasma treatment on the surface of a thermoplastic saturated norbornene-based polymer molded product in advance, an ultraviolet curing agent was added. It has been found that the above object can be achieved by forming a cured layer by using the composition.

That is, after performing a plasma treatment on the surface of a thermoplastic saturated norbornene-based polymer molded article, an ultraviolet curing agent is applied, and then a cured layer is formed by irradiating ultraviolet rays, whereby the adhesive strength is excellent and the hardness is high. A cured layer having a high hardness is obtained. According to this method, the intended purpose can be achieved even if a solvent-free ultraviolet curing agent is used, so that the amount of the residual solvent in the cured layer can be significantly reduced or eliminated.

According to this method, a durability promotion test under high temperature and high humidity conditions (for example, 60 ° C., 80% RH, 100 hours)
Even afterwards, high adhesive strength can be maintained.
Also, before, after or before or after the plasma treatment, an ion shower treatment is performed to remove static charges on the surface, so that the adhesive strength can be further increased. Further, when the temperature of the surface of the molded article at the time of ultraviolet irradiation is set to 40 ° C. or higher, the adhesive strength can be further increased. The present invention has been completed based on these findings.

[0011]

According to the present invention, a surface of a thermoplastic saturated norbornene-based polymer molded article is preliminarily subjected to plasma treatment, an ultraviolet curing agent is applied, and then cured by irradiating ultraviolet rays. Provided are a thermoplastic saturated norbornene-based polymer molded article having a cured layer characterized by forming a layer, and a method for producing the same.

In this case, before or after the plasma treatment, before or after the plasma treatment, static electricity is removed by an ion shower, and / or the maximum temperature of the molded article on the surface to which the ultraviolet curing agent is applied is kept at 40 ° C. or more. By irradiating with ultraviolet rays, a manufacturing method for further improving the adhesive strength of the cured layer is provided.

Hereinafter, the present invention will be described in detail. (Thermoplastic saturated norbornene-based polymer) Specific examples of the thermoplastic saturated norbornene-based polymer used in the present invention include a hydrogenated product of a ring-opened polymer of a norbornene-based monomer, an addition-type polymer of a norbornene-based monomer, or a norbornene-based monomer and an olefin. Can be mentioned.

The hydrogenated product of a ring-opened polymer of a norbornene-based monomer includes, as monomers, for example, norbornene and its alkyl and / or alkylidene-substituted products, for example, 5-methyl-2-norbornene, 5,6
-Dimethyl-2-norbornene, 5-ethyl-2-norbornene, 5-butyl-2-norbornene, 5-ethylidene-2-norbornene and the like, and substituted polar groups such as halogens; dicyclopentadiene, 2,3- Dihydrodicyclopentadiene or the like; dimethanooctahydronaphthalene, an alkyl and / or alkylidene-substituted product thereof,
And polar group substituents such as halogen, for example, 6-methyl-1,4: 5,8-dimetano-1,4,4a, 5,6.
7,8,8a-octahydronaphthalene, 6-ethyl-
1,4: 5,8-dimethano-1,4,4a, 5,6
7,8,8a-octahydronaphthalene, 6-ethylidene-1,4: 5,8-dimethano-1,4,4a, 5
6,7,8,8a-octahydronaphthalene, 6-chloro-1,4: 5,8-dimetano-1,4,4a, 5
6,7,8,8a-octahydronaphthalene, 6-cyano-1,4: 5,8-dimethano-1,4,4a, 5
6,7,8,8a-octahydronaphthalene, 6-pyridyl-1,4: 5,8-dimethano-1,4,4a, 5
6,7,8,8a-octahydronaphthalene, 6-methoxycarbonyl-1,4: 5,8-dimethano-1,4,
4a, 5,6,7,8,8a-octahydronaphthalene or the like; cyclopentadiene trimer or tetramer, for example, 4,
9: 5,8-Dimethano-3a, 4,4a, 5,8,8
a, 9,9a-octahydro-1H-benzoindene,
4,11: 5,10: 6,9-trimethano-3a, 4,4
4a, 5, 5a, 6, 9, 9a, 10, 10a, 11,
11a-dodecahydro-1H-cyclopentaanthracene; and the like, to obtain a substantially saturated polymer produced by subjecting a ring-opened polymer obtained by polymerization by a known ring-opening polymerization method to hydrogenation by an ordinary hydrogenation method. Polymer.

The addition polymer of a norbornene monomer is a polymer obtained by addition polymerization of a norbornene monomer as described above as a monomer and / or a hydrogenated product thereof. The addition polymer of a norbornene monomer and an olefin is As the monomer, a polymer and / or a hydrogenated product thereof obtained by addition-copolymerizing a norbornene-based monomer as described above and an olefin such as ethylene or propylene by a known method,
Both are substantially saturated polymers.

The suitable range of the molecular weight of the thermoplastic saturated norbornene polymer is from 10,000 to 200,000 as a number average molecular weight measured by GPC (gel permeation chromatography) analysis using toluene as a solvent. When the unsaturated bonds remaining in the molecular chain are saturated by a hydrogenation reaction, the hydrogenation rate is preferably 90% or more, more preferably 95% or more, and still more preferably from the viewpoint of light resistance and weather resistance. Is 99% or more. The thermoplastic saturated norbornene-based polymer is converted into α-
It may be a copolymer of other monomer components such as olefin and cycloolefin.

The thermoplastic saturated norbornene polymer used in the present invention may optionally contain other resins, antistatic agents, antioxidants, fillers such as glass fibers, dyes, and the like.
Additives such as pigments can be blended.

There are no particular restrictions on the molding method of the molded article of the thermoplastic saturated norbornene-based polymer, for example, those obtained by injection molding such as optical disks and lenses,
Examples include a sheet or film melt-extruded into a tube or rod, a sheet or film melt-extruded and wound by a roll, a sheet formed by hot pressing, a film obtained by casting a solvent solution, and a stretched film by stretching. Can be

(Plasma Treatment) Generally, in the field of painting and printing, surface treatment has been studied for a long time in order to improve the adhesion of poorly adherent polymers such as polyolefins and polyesters. Various methods such as treatment methods, solvent treatment methods, primer methods, polymer coating methods, coupling agent treatment methods, surfactant treatment methods, back surface grafting methods, colloid treatment methods, ultraviolet irradiation treatment methods, and plasma treatment methods have been proposed. (Edited by the Society of Materials Technology, "Handbook for Painting and Printing Plastics", Chapter V, "Surface Treatment of Plastic Molded Articles for Painting",
Published by Sogo Gijutsu Publisher, published on December 10, 1973,
p. 142-172) In these surface treatment methods, generally, a polar functional group such as a carbonyl group or a hydroxyl group is introduced in the vicinity of the surface of the polymer, thereby imparting or improving the adhesive force. However, the surface treatment method greatly depends on the type of surface treatment, the constituent elements and molecular structure of the target polymer, the material of the substance to be adhered to the polymer surface, and the like. Not all of these surface treatment methods are effective for any polymer. Even if the surface treatment is performed, the modifying effect may not be obtained, or the polymer may be deteriorated. Therefore, what kind of surface treatment is to be performed for which polymer is a technically important issue, and requires some contrivance.

Conventionally, a cured layer is formed on the surface of a thermoplastic saturated norbornene-based polymer molded article after a surface treatment in advance. In particular, after plasma treatment, an ultraviolet curing agent is used to achieve high adhesive strength and hardness. It has not been proposed to form a cured layer having the same.

The present inventors have studied various surface treatment methods to improve the adhesive strength of the thermoplastic saturated norbornene-based polymer molded article to the cured layer. As a result, most of the surface treatment methods have no particular effect. When the plasma treatment is performed, the wettability and adhesion with the ultraviolet curing agent are improved,
It has been found that a cured layer having practical adhesive strength and hardness can be formed.

The plasma treatment is usually performed at 10 ^{−2 to} 10 T
A glow discharge of a low-pressure gas of orr (argon, oxygen, nitrogen, or the like) is used. By this treatment, the surface modification of the thermoplastic saturated norbornene-based polymer molded article can be effectively performed. Specifically, for example, the molded product is 0.1%
The surface modification effect can be achieved by exposing it to a plasma atmosphere of oxygen gas at a pressure of about Torr for several seconds. The plasma treatment is a dry process and is effective in a short time, and thus has excellent productivity.

(Electrostatic Static Elimination Treatment) When the static electricity elimination treatment of the surface of the molded article is performed by an ion shower together with the plasma treatment, the adhesive strength between the molded article and the cured layer can be further improved. The ion shower refers to a process of ionizing gas molecules in the air and blowing the gas molecules in a breeze shape to remove static charges on the surface of a material that is easily charged. Usually, it is used for dust prevention, but this treatment alone does not result in surface modification of the poorly adhesive material. The static electricity elimination treatment by the ion shower is performed before, after or before or after the surface treatment and before the application of the ultraviolet curing agent.

(Ultraviolet curing agent) The ultraviolet curing agent used in the present invention comprises a reactive monomer and / or a reactive oligomer and a photopolymerization initiator as essential components, and includes an acrylic photopolymerizable composition. .

As the reactive monomer, acrylates are the main ones. Specifically, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-ethylhexyl methacrylate, phenoxyethyl acrylate, phenoxypropyl acrylate, Other monofunctional acrylate monomers such as higher alkyl acrylates; other monofunctional monomers such as styrene and vinylpyrrolidone; ethylene glycol, diethylene glycol, tripropylene glycol, butylene glycol, hexanediol, trimethylolpropane, tetramethylolpropane, and pentane Polyfunctional acrylate monomers in which two or more acrylates are bonded to a polyol such as erythritol; and the like.

The reactive oligomer includes polyester acrylate having an acroyl group at the terminal, epoxy acrylate or polyurethane acrylate having an epoxy group in the molecular chain and an acroyl group at the terminal, unsaturated polyester having a double bond in the molecular chain, Examples thereof include 1,2-polybutadiene and other oligomers having an epoxy group or a vinyl ether group.

Examples of the photopolymerization initiator include acetophenones such as 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, and chlorinated acetophenone; benzophenones; benzyl, methylorthobenzoylbenzoate, and benzoin alkyl ether. Azo compounds such as α, α'-azobisisobutyronitrile, 2,2'-azobispropane and hydrazone; organic peroxides such as benzoyl peroxide and ditertiary butyl peroxide; diphenyldi Diphenyl disulfides such as sulfide, dibenzyl disulfide and dibenzoyl disulfide; and the like.

To the ultraviolet curing agent, a suitable thermoplastic polymer may be added for the purpose of adjusting the viscosity or improving the adhesive strength. In general, polymers with similar structures have good compatibility and good wettability, so if a thermoplastic polymer is added for the purpose of improving the adhesion, a ring-opening polymer of a norbornene-based monomer can be used. It is effective to use a hydrogenated product, an addition-type polymer of a norbornene-based monomer, or a polymer having a structure similar to that of an addition-type copolymer of a norbornene-based monomer and an olefin. Specifically, a hydrogenated product of a ring-opening polymer of a norbornene-based monomer, an addition-type polymer of a norbornene-based monomer, or an addition-type copolymer of a norbornene-based monomer and an olefin itself, dicyclopentadiene-based, diene-based, aliphatic-based, Aromatic and water white petroleum resins and hydrogenated products thereof are suitable. However, if a large amount of the non-reactive thermoplastic polymer is added, the photosensitivity to ultraviolet rays is undesirably reduced.

Further, various surfactants for improving the surface chargeability and other properties may be added. In this case, a surfactant which is transparent and has good compatibility with the curing agent, specifically, a nonionic surfactant, particularly an amine surfactant is suitable. In addition, a thermal polymerization inhibitor, a photopolymerization inhibitor, a tackifier, a filler, and the like may be appropriately used. The ultraviolet curing agent may be appropriately diluted with a solvent. However, in a field where a residual solvent is a problem, it is preferable to use a solvent-free solvent.

In order to form a cured layer, an ultraviolet curing agent is applied to a molded article made of a thermoplastic saturated norbornene-based polymer, and when a solvent is contained, the solvent is removed by drying, followed by irradiation with ultraviolet rays.

There are no particular restrictions on the coating conditions, and all coating methods such as spraying, dipping, spin coating, roll coater, and brush coating are possible. The thickness to apply is 2 ~
The thickness is preferably 300 μm (when a solvent is contained, the thickness after drying). If the thickness is smaller than this range, a hardened layer having high strength cannot be obtained, and a sufficient effect of improving the surface hardness may not be obtained. If it is thicker than this range,
It takes time for the drying and curing reaction, resulting in poor productivity.
In addition, the cured layer may be insufficiently cured and the strength of the cured layer may be lower than the case where it is thin, or the cured layer may be too hard and crack.

When a solvent is used, it is necessary to sufficiently dry the coated surface. If the coating is cured while containing a large amount of solvent, cracks are likely to occur in the coating film, which may cause a hardened layer with high hardness to not be obtained, and increase the residual solvent amount. The drying temperature and time depend on the type of solvent used,
Although it differs depending on the shape of the bonding surface, the conditions may be determined so that the substrate is not more than 120 ° C. and sufficiently dried so that the substrate is not thermally deformed. Specifically, 60-1
Drying at 20 ° C. for about 3 to 60 minutes is appropriate. After drying at a high temperature, it is preferable to perform cooling at room temperature for about 10 seconds to 10 minutes, and to cool to about room temperature.

However, the cured layer obtained in this manner, even after being sufficiently dried, retains a small amount of the solvent used for the ultraviolet curing agent, and as a result, the characteristics of the cured layer change with time. In some cases, or the residual solvent is gradually diffused from the surface, which may adversely affect other surrounding materials.

(Ultraviolet irradiation) After a curing agent is applied to the surface of the molded article, the ultraviolet light is irradiated from a light source such as a high-pressure mercury lamp or a metal halide lamp which efficiently generates ultraviolet light, whereby curing occurs in a short time and the hardness is reduced. A high cured layer is formed. The irradiation amount of the ultraviolet ray varies depending on the type of the reactive monomer or the reactive oligomer, the reactivity of the photopolymerization initiator, and the like. Usually, in the case of a high-pressure mercury lamp of 80 W / cm, the irradiation distance is 10 cm or less for 60 seconds or less. It can be cured in a short time of about 5 to 10 seconds.

Conventionally, when a cured layer made of an ultraviolet curing agent is formed on the surface of a plastic molded product, the ultraviolet irradiation is performed using a cold mirror or the like so that the temperature of the irradiated surface does not rise. However, the inventors of the present invention have studied that, in the formation of a cured layer on the surface of a thermoplastic saturated norbornene-based polymer molded product using an ultraviolet curing agent, if the surface (application surface) temperature during ultraviolet irradiation is increased, the It has been found that the adhesive strength increases. Therefore, when the temperature of the application surface of the molded article subjected to the plasma treatment is increased and the ultraviolet ray is irradiated, the adhesive strength is greatly increased due to a synergistic effect.

When the temperature of the coating surface (irradiation surface) at the time of ultraviolet irradiation is increased, the temperature is set to 40 ° C. or higher, preferably 50 ° C. or higher. The upper limit is the temperature at which the molded product does not thermally deform,
From the viewpoint of workability and the like, the temperature is preferably about 80 ° C, more preferably about 70 ° C. The temperature of the irradiation surface is, for example,
The term “40 ° C.” means a temperature at which the maximum temperature during irradiation is 40 ° C.

The method for raising the temperature during irradiation to 40 ° C. or higher is not particularly limited. For example, ultraviolet rays may be irradiated using a type of ultraviolet lamp without a cold mirror.
Alternatively, they may be used in combination for heating. If you only use a lamp without a cold mirror,
Since the temperature changes depending on the distance from the lamp, the irradiation time, and the like, it is necessary to adjust them. For example, 80W
When a high-pressure mercury lamp of / cm is used, the distance between the lamp and the irradiation surface may be 15 cm and irradiation may be performed for about 20 seconds or more.

(Molded Article Having a Cured Layer) The thermoplastic saturated norbornene-based polymer molded article having a cured layer obtained by the production method of the present invention has excellent adhesive strength between the molded article and a cured layer formed by an ultraviolet curing agent, and Since it has a hardened layer on the surface, it has a high surface hardness. Adhesion strength by Goban test is at least 60% or more, and pencil hardness is 2
H or more, usually about 3H.

In general, the adhesive strength between the cured layer and the plastic substrate is preferably, for example, 90% or more according to the Gobang test, but according to the production method of the present invention,
It is also possible to obtain 95 to 100%. Also,
In order to maintain the adhesive strength for a long period of time, the conditions for promoting the durability under high temperature and high humidity conditions (for example, 60 ° C., 80% RH,
Even at 0 hour), it is desirable to maintain an adhesive strength of 90% or more in the Goban test, but according to the production method of the present invention, such a high level of performance can be achieved.

The production method of the present invention is suitable for forming an optical material using a thermoplastic norbornene-based polymer as a substrate. For example, formation of a protective coat layer for protecting the recording layer of the optical information disc, formation of a hardened layer for protecting the exposed portion of the substrate on the back of the recording layer, and supplementing the surface hardness of the optical lens and other optical components. It is suitable for forming a cured layer for protecting the surface.

Further, adhesion between the thermoplastic saturated norbornene-based polymer and other materials is performed by using an ultraviolet curing agent (acrylic photopolymerizable composition), or as in the case of cutting an optical lens. The production method of the present invention is also applicable to flattening the surface of a thermoplastic saturated norbornene-based polymer using an ultraviolet curing agent.

[0042]

EXAMPLES The present invention will be specifically described below with reference to examples, reference examples and comparative examples, but the present invention is not limited to the examples. In addition, the physical property measuring method is as follows.

<Gobang test> 11 cuts each in the vertical and horizontal directions were made at intervals of 1 mm with a cutter from the hardened layer formed on the surface of the molded product, and a square of 1 mm square was formed.
Cellophane adhesive tape (Sekisui Chemical Co., Ltd.
The adhesive tape was peeled in the 90 ° direction, and the number of eyes that did not peel was expressed in%.

<Durability test> The test piece on which the hardened layer was formed
After keeping at 0 ° C. and 80% RH for 100 hours, a Goban test was performed.

<Pencil hardness> Measured under a load of 1 kg according to JIS K-5400.

<Amount of Residual Solvent> Measured at 200 ° C. by gas chromatography.

[Reference Example 1] (Test piece preparation example 1) 6-methyl-1,4: 5,8-dimethano-1,4,4
a, 5,6,7,8,8a-Hydrogenated ring-opened polymer of octahydronaphthalene (MTD) (number average molecular weight 28,
000, hydrogenation rate almost 100%, glass transition temperature 152
C.) to form a disc (base material 1) having a thickness of 2 mm and a diameter of 100 mm. The pencil hardness of this molded product is 2H
Met.

Reference Example 2 (Test piece preparation example 2) A copolymer obtained by ring-opening polymerization of a mixed monomer of MTD and dicyclopentadiene (DCP) (MTD / DCP = 70/30 molar ratio) Hydrogenated product (number average molecular weight 27,00
0, a hydrogenation rate of almost 100%, and a glass transition temperature of 133 ° C.), and a disk (substrate 2) similar to that of Reference Example 1 was prepared. The pencil hardness of the surface of this molded product was H.

Reference Example 3 (Preparation Example of Curing Agent) The following components were mixed and stirred to prepare an ultraviolet curing agent. Dipentaerythritol hexaacrylate (DPEHA) 70 g Methyl acrylate (MA) 30 g Photopolymerization initiator (* 1) 3 g (* 1) Benzyldimethylketal; trade name Irgacure 651 manufactured by Ciba-Geigy

Example 1 The disk (substrate 1) prepared in Reference Example 1 was subjected to an ion shower for 5 seconds at a distance of 10 cm using a 495-type ion shower apparatus manufactured by Hakko Metal Industry Co., Ltd. , Low pressure glow discharge treatment, 0.1 Torr
The treatment was performed with oxygen plasma of r, and ion shower was further performed under the same conditions as above. The hardening agent prepared in Reference Example 3 was applied to the surface-treated disk by spin coating (3,000 rotations, 80 seconds). The thickness of the coating layer was 6 μm.

Then, the coated surface was cured by irradiating ultraviolet rays with a high pressure mercury lamp of 80 W / cm for a distance of 20 cm and an irradiation time of 60 seconds without a cold mirror. The maximum temperature of the coated surface during irradiation was 50 ° C. The obtained disc having a cured layer has an adhesion strength of 100% according to the Gobang test.
The pencil strength was 3H, the amount of residual solvent was 0.00%, and the adhesive strength after the durability test was 93%.

[Examples 2 to 7, Comparative Examples 1 to 6] Under the conditions shown in Table 1, the base materials prepared in Reference Examples 1 and 2 and Reference Example 3
Using the curing agent prepared in the above, a molded article having a cured layer was prepared, and the physical properties were measured. The results are collectively shown in Table 1. In addition, each operation and processing are as follows.

Coating method: spin coating, 3,000 revolutions,
80 seconds, thickness 6 μm. Ion shower: Model 495 manufactured by Hakoko Metal Industry Co., Ltd., exposed at a distance of 10 cm for 5 seconds. UV irradiation: 80 W / cm high pressure mercury lamp, distance 20 cm,
Irradiation time 60 seconds. Surface treatment a: plasma treatment, low-pressure glow discharge treatment, 0.
Treated with 1 Torr oxygen plasma.

Surface treatment b: washing with Freon R-113, immersion for 30 seconds. Surface treatment c: methyl isobutyl ketone / toluene (98
/ 2 weight ratio) mixed solvent treatment, immersion 5 seconds. Surface treatment d: treatment with a silane coupling agent, immersion in a vinyl (trimethoxy) silane / acetone (5/95 weight ratio) solution for 5 seconds, and treatment in an oven at 90 ° C. for 2 hours. Surface treatment e: UV irradiation, 80 W / cm high pressure mercury lamp, distance 20 cm, irradiation time 60 seconds. The thickness of the cured layer was measured using a stylus-type film thickness meter (Alpha Step 200, manufactured by Tenker Corporation).

[0055]

[Table 1]

As is clear from Table 1, the plasma treatment of the present invention can provide a molded article having a cured layer in which the adhesive strength, surface hardness, residual solvent amount, and adhesive strength after the durability test have all been improved. I understand. In particular, a remarkable improvement effect can be obtained by combining the plasma treatment of the present invention and maintaining the irradiated surface at a high temperature, or by further performing an ion shower. On the other hand, when the plasma treatment is not performed, in addition to the case where the solvent treatment method, the coupling agent treatment method, and the other surface treatment method such as the ultraviolet irradiation treatment method are employed, the adhesive strength is not improved at all, The improvement effect is extremely insufficient.

[0057]

According to the present invention, there is provided a norbornene-based polymer molded article having a cured layer having excellent adhesive strength and high hardness, and a method for producing the same. ADVANTAGE OF THE INVENTION According to this invention, the adhesive strength after a durability test is favorable, and formation of the hardened layer which reduced or eliminated the residual solvent is possible.

────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kotaro Hataba 234-1, Konakacho, Sano-shi, Tochigi Prefecture Optes Co., Ltd. (56) References JP-A-4-93334 (JP, A) JP-A-4-89217 (JP, A) JP-A-3-223341 (JP, A) JP-A-3-95235 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08J 7/00-7 / 18

Claims (4)

(57) [Claims] 1. A cured layer formed by subjecting a surface of a thermoplastic saturated norbornene polymer molded article to plasma treatment in advance, applying an ultraviolet curing agent, and then irradiating ultraviolet rays to form a cured layer. A method for producing a thermoplastic saturated norbornene-based polymer molded article having: 2. The manufacturing method according to claim 1, wherein before, after, before or after the plasma treatment, static electricity is removed by an ion shower. 3. The method according to claim 1, wherein the ultraviolet ray is radiated while controlling the maximum temperature of the molded article to which the ultraviolet curable agent is applied, to 40 ° C. or higher. 4. A thermoplastic saturated norbornene-based polymer having a cured layer formed by subjecting a surface of a thermoplastic saturated norbornene-based polymer molded article to plasma treatment in advance, applying an ultraviolet curing agent, and then irradiating ultraviolet rays. Molding